• Mononuclear non-heme iron(III) complexes of linear and tripodal tridentate ligands as functional models for catechol dioxygenases: Effect of 𝑁-alkyl substitution on regioselectivity and reaction rate

    • Fulltext

       

        Click here to view fulltext PDF


      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/123/02/0145-0162

    • Keywords

       

      Catechol dioxygenases; functional models; mononuclear iron(III) complexes; Lewis acidity; regioselectivity.

    • Abstract

       

      Catechol dioxygenases are responsible for the last step in the biodegradation of aromatic molecules in the environment. The iron(II) active site in the extradiol-cleaving enzymes cleaves the C-C bond adjacent to the hydroxyl group, while the iron(III) active site in the intradiol-cleaving enzymes cleaves the C-C bond in between two hydroxyl groups. A series of mononuclear iron(III) complexes of the type [Fe(L)Cl3], where L is the linear 𝑁-alkyl substituted bis(pyrid-2-ylmethyl)amine, 𝑁-alkyl substituted 𝑁-(pyrid-2-ylmethyl)ethylenediamine, linear tridentate 3N ligands containing imidazolyl moieties and tripodal ligands containing pyrazolyl moieties have been isolated and studied as structural and functional models for catechol dioxygenase enzymes. All the complexes catalyse the cleavage of catechols using molecular oxygen to afford both intra- and extradiol cleavage products. The rate of oxygenation depends on the solvent and the Lewis acidity of iron(III) center as modified by the sterically demanding 𝑁-alkyl groups. Also, our studies reveal that stereo-electronic factors like the Lewis acidity of the iron(III) center and the steric demand of ligands, as regulated by the 𝑁-alkyl substituents, determine the regioselectivity and the rate of dioxygenation. In sharp contrast to all these complexes, the pyrazole-containing tripodal ligand complexes yield mainly the oxidized product benzoquinone.

    • Author Affiliations

       

      Mallayan Palaniandavar1 Kusalendiran Visvaganesan1

      1. Centre for Bioinorganic Chemistry, School of Chemistry, Bharathidasan University, Tiruchirappallli 620 024, India
    • Dates

       
  • Journal of Chemical Sciences | News

© 2017-2019 Indian Academy of Sciences, Bengaluru.